Ethyl chloroformate → 7-Nitro-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid ethyl ester

HRID 925229ノート

反応式

HRID 925229 の反応式
[N+:1]([C:4]1[CH:14]=[CH:13][C:7]2[CH2:8][CH2:9][NH:10][CH2:11][CH2:12][C:6]=2[CH:5]=1)([O-:3])=[O:2].CCN(C(C)C)C(C)C.Cl[C:25]([O:27][CH2:28][CH3:29])=[O:26]>C(Cl)Cl.Cl>[CH2:28]([O:27][C:25]([N:10]1[CH2:11][CH2:12][C:6]2[CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:14]=[CH:13][C:7]=2[CH2:8][CH2:9]1)=[O:26])[CH3:29]

参加物

6

反応物 3

HCID 10928Ethyl chloroformateHCID 81531DiisopropylethylamineHCID 113100427-Nitro-2,3,4,5-tetrahydro-1H-benzo[D]azepine

生成物 1

HCID 584953837-Nitro-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid ethyl ester

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

To a stirred solution of the product from Example 36, step (a) (5 g, 26.0 mmol) dissolved in DCM (75 ml), DIEA (6.8 ml, 39 mmol) was added. The reaction mixture was cooled to 0° C. and ethyl chloroformate was added (3.0 ml, 31.2 mmol). The reaction mixture was stirred at 0° C. for 2 hours and then allowed to warm to room temperature. The reaction mixture was diluted with 2N HCl (150 ml) and extracted with DCM (3×). The combined DCM extracts were washed with brine, dried over Na2SO4, and solvent evaporated in vacuo to give the crude product. Purification by silica-gel chromatography (gradient elution: 0 to 50% EtOAc in hexane) gave the sub-title compound as a light yellow solid (4.7 g). 1H NMR (300 MHz, DMSO-d6) δ 8.07 (d, J=2.4 Hz, 1H); 8.01 (dd, J=8.1 Hz, 2.4 Hz, 1H); 7.45 (d, J=8.1 Hz, 1H); 4.07 (q, J=6.9 Hz, 2H); 3.54-3.51 (m, 4H); 3.04-3.01 (m, 4H); 1.19 (t, J=7.2 Hz, 3H).

後処理

  1. temperatureto warm to room temperature
  2. extractionextracted with DCM (3×)
  3. washThe combined DCM extracts were washed with brine
  4. dry with materialdried over Na2SO4, and solvent
  5. customevaporated in vacuo
  6. customto give the crude product
  7. customPurification
  8. washby silica-gel chromatography (gradient elution: 0 to 50% EtOAc in hexane)

出典と根拠

ORDレコード
ord-cbb657eccd994f81a6d8e52d8e970240
出典データセット
uspto-grants-2016_03
特許番号
US09284277B2

反応ノート

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